JPH06263863A - Heterocyclic bis(4-hydroxyphenyl)cycloalkane and polycarbonate produced therefrom - Google Patents

Abstract

PURPOSE: To obtain a polycarbonate which has a high glass transition temperature and is expected to be ductile by reacting a specified heterocyclic bisphenol with a known carbonate source.

CONSTITUTION: A heterocyclohexylidene bisphenol of formula I (wherein X is S, SO, SO₂ or N-OCOR; and R is a 1-4C primary or secondary alkyl or a 6-8C aromatic group) is reacted with a carbonate source such as phosgene or dimethyl carbonate by a common technique to obtain a polycarbonate comprising heterocyclohexylidene bisphenol structural units of formula II (wherein X is as defined above). A series of the above polycarbonates have Tgs higher than the Tg of bisphenol A polycarbonate by 35-84°C and are expected to be ductile. A bisphenol of formula I (wherein X is S or N-OCOR) can be obtained by reacting phenol with tetrahydrothiopyran-4-one or an acylated 4-piperidone in the presence of an acid catalyst.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to materials of new composition, in particular new polycarbonates and their precursors.

[0002]

Polycarbonates are a group of high performance engineering resins characterized by possessing optical clarity, high ductility and other advantageous properties. Due to their transparency, these resins are often used as lenses and windows. Bisphenol A polycarbonate is the major commercially available resin of this type. This resin is derived from 2,2-bis (4-hydroxyphenyl) propane and typically has a glass transition temperature of about 150 ° C.

There is increasing interest in the production of polycarbonates which have a higher glass transition temperature while retaining the ductility of bisphenol A polycarbonate and therefore a higher resistance to softening on heating. A typical area of use of such polycarbonates is the manufacture of lenses for automotive headlamps-these lenses are becoming smaller and smaller in size, so they are placed closer to the heat-generating light source. And-windows for aircraft operating at high altitudes-in which case the effects of solar heat may be significant.

[0004]

SUMMARY OF THE INVENTION The present invention is at least 35 ° C to 84 ° C above the glass transition temperature of bisphenol A polycarbonate.
It provides a group of polycarbonates which have a high glass transition temperature up to ℃ and are expected to be ductile. The present invention also provides a series of bisphenols that can be converted to the polycarbonate.

According to one aspect of the invention, the invention has the formula:

[0006]

[Chemical 3]

(In the formula, X is S, SO, SO ₂ or N--O
COR and R is a C _1-4 primary or secondary alkyl group or a C _6-8 aromatic group) heterocyclic bis (4-hydroxyphenyl) cycloalkane (hereinafter, optionally (Simply called "heterocyclic bisphenol")
Includes. The X group in the heterocyclic bisphenol of the present invention may be a sulfur, sulfone group or acylated nitrogen atom. In the acylated nitrogen atom, R is an alkyl group such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methylpropyl group or an aromatic group such as phenyl, tolyl or xylyl group. It can be a group. A methyl group is preferred.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The heterocyclic bisphenol of the present invention in which X is a sulfur or acylated nitrogen atom is obtained by reacting phenol and tetrahydrothiopyran-4-one or acylated 4-piperidone in the presence of an acidic catalyst. It can be produced by reacting with. Further, it is preferable that mercaptan is also present as a reaction accelerator. The heterocyclic bisphenol wherein X is sulfur can be prepared by oxidation with a suitable oxidizing agent, eg in an acidic medium, typically glacial acetic acid,
Oxidation with a percarboxylic acid such as peracetic acid can be converted to the corresponding heterocyclic bisphenol compound where X is SO and / or SO ₂ .

Next, production of the heterocyclic bisphenol of the present invention will be described with reference to examples. The molecular structure is ¹ H and
^It was determined by ¹³ C nuclear magnetic resonance spectral analysis and mass spectral analysis. Example 1 Tetrahydrothiopyran-4-one 10 g (86 mmol), phenol 81 g (860 mmol) and hydrogen ion concentration of 4 meq / g, 0.8 meq / g
A mixture of 10 g of an acid type cation exchange resin modified with a thiol accelerator in the ratio of was heated at 75 ° C. for 4 hours. The resulting orange solution was hot filtered through a glass funnel. On cooling a solid formed which was separated by filtration. When the filtrate was mixed with 100 ml of methylene chloride, a second solid matter was deposited and collected by filtration.

The total amount of these crude solids is 28.6 g
Met. These were recrystallized from chlorobenzene to obtain the desired 4,4-bis (4-hydroxyphenyl) thiopyran as light tan crystals. The yield was 18.35 g (75% of theory). Example 2 A mixture of 100 g (1.06 mol) of phenol and 3 ml of dodecylthiol was heated to 50 ° C under a nitrogen atmosphere,
Gaseous hydrogen chloride was then bubbled through the mixture for 15 minutes. 1-acetyl-4-piperidone 1 for hydrogen chloride
Continued while 5 g (106 mmol) was added over 5 minutes. The hydrogen chloride treatment was continued for 20 minutes and then the mixture was stirred at 75 ° C. for 20 hours. It was then cooled to room temperature and diluted with ethyl acetate and saturated sodium hydrogen carbonate solution to precipitate the crude product as a white solid. It was collected by filtration and washed with water until neutral. The yield of crude product was 25.9 g (78% of theory). A portion of this crude product was recrystallized from glacial acetic acid and the desired 4,4-bis (4-hydroxyphenyl)-
It was identified as 1-acetylpiperidine. Example 3 A slurry of 5 g (17 mmol) of the product of Example 1 in 20 ml glacial acetic acid is added to 8.86 g (37.2 mmol) of a 32 wt% solution of peracetic acid in glacial acetic acid over 20 minutes at ice bath temperature. Added. The mixture became warm for 14 hours to room temperature and became opaque. The precipitated solid was filtered through a glass funnel and washed twice with glacial acetic acid. Desired 4,4-
The crude product yield of bis (4-hydroxyphenyl) pentamethylene sulfone was 4.25 g (77% of theory). The product was recrystallized from methanol and water to give 3.5 g (63% of theory) of pure product.

The heterocyclic bisphenols of this invention can be converted to polycarbonates by reacting with phosgene or a carbonate source such as dimethyl carbonate using conventional techniques. These techniques include melt polymerization, interfacial polymerization and interfacial conversion to bischloroformate followed by polymerization. Chain terminators such as phenols may also be used.

Such polycarbonate constitutes another aspect of the present invention. These are the formulas:

[0013]

[Chemical 4]

It comprises a heterocyclohexylidene bisphenol structural unit of the formula wherein X has the abovementioned meaning. Polycarbonates of the invention where X is SO and / or SO ₂ may also be prepared from the corresponding polycarbonate where X is S by oxidation with a suitable oxidant, typically a peracid.

The polycarbonates of the present invention include both homopolycarbonates and copolycarbonates. The copolycarbonate may contain structural units of more than one molecular species of heterocyclohexylidene bisphenol.
Copolycarbonates also contain units corresponding to the dihydroxy compounds disclosed by name or formula (general or specific) in US Pat. No. 4,217,438, which is incorporated herein by reference. You can Such copolycarbonates are typically about 25-75% by number.
It contains (% based on the number of units) bis (4-hydroxybiphenylyl) alkane units with the balance being other units.

The other units are of the formula: (Wherein each of A ¹ and A ² is a monocyclic divalent aromatic group and Y is A ¹ to A ² depending on one or two atoms.
A unit having a bridging group of the type which separates from). The free valence bond in formula (III) is usually A ^{1 with} respect to Y.
And in the meta or para position of A ² .

The A ¹ and A ² groups can be unsubstituted phenylene groups or substituted derivative groups thereof. Examples of the substituent (s) are alkyl, alkenyl, halo (especially chloro and / or bromo), nitro, alkoxy groups and the like. Unsubstituted phenylene groups are preferred. Group A ¹
And A ² are both p-phenylene groups, but both may be o- or m-phenylene groups, or one is an o- or m-phenylene group and the other is a p-phenylene group. Can also be

The bridging group Y is a bridging group of the type which separates A ¹ from A ² by 1 or 2 atoms, preferably 1 atom. The bridging groups are often hydrocarbon groups, especially saturated hydrocarbon groups such as methylene, cyclohexylmethylene, 2- [2.2.1] -bicycloheptylmethylene,
It is an ethylene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene group, especially a gem-alkylene (alkylidene) group. However, unsaturated groups and groups containing atoms other than carbon and hydrogen, such as 2,2
-Dichloroethylidene, carbonyl, phthalidylidene,
Also included are oxy, thio, sulfoxy and sulfone groups. The preferred units of formula (III) are 2,2-bis (4) because of their ready availability and particular suitability for the purposes of the present invention.
- phenylene) propane carbonate units, i.e. are derived from bisphenol A, Y is isopropylidene and A ¹ and A ² is a unit, are each p- phenylene.

The production of the polycarbonates of the invention is illustrated by the following examples. The molecular weight was measured by gel permeation chromatography using polystyrene as a standard. Examples 4-9 Various bisphenol mixtures were mixed at a rate of 8.42 w / v% with methylene chloride and with the following vol% other materials. All percentages used herein are based on the methylene chloride.

Water—5 w / v% triethylamine solution in 90% methylene chloride—
1.5% 5w / v% phenol solution in methylene chloride-2% Phosgene was passed into this mixture for 10 minutes under stirring for a total of 6w / v% while the pH value of the aqueous phase was 10% water. A value of 10 to 11 was maintained by the addition of aqueous sodium oxide solution. The mixture was then purged with nitrogen for 15 minutes and the organic phase separated, washed twice with 3% aqueous hydrochloric acid solution, then four times with water and dried over magnesium sulfate. The dried solution was poured into methanol and the precipitated solid was redissolved in methylene chloride, precipitated by addition of acetonitrile, redissolved in methylene chloride and reprecipitated by addition of methanol. The resulting copolycarbonate was dried to constant weight.
The nature (composition) and properties of these are shown in the following table.

Example Bisphenol, mol% Mw Mw / Mn Tg. ° C. 4 Example 1 100 50,000 1.91 209 5 Example 1 50 90,500 1.68 186 Bisphenol A 50 6 Example 1 50 ―――― 234 Example 3 50 7 Example 2 100 --- 22 18 Example 2 50 70,000 1.74 207 Bisphenol A 50 9 Example 3 50 50,800 1.57 185 Bisphenol A 50 3.5 w / v% dilute solution of bisphenol A in methylene chloride and Similar results were obtained using triethylamine, phenol and phosgene in low proportions of 0.75%, 1% and 3% respectively. Example 10 300 mg of the polycarbonate of Example 4 and 116 mg of m-chloroperbenzoic acid in 50 ml of methylene chloride (0.
67 mmol) solution was stirred at room temperature for 1 hour, after which the product was isolated by precipitation into methanol, filtration and drying in a vacuum oven. The product was the desired heterocyclohexylidene bisphenol sulfoxide / sulfone copolycarbonate and had a glass transition temperature of 283 ° C.

Claims (18)

[Claims] 1. The formula: Where X is S, SO, SO ₂ or N-OCOR and R is a C _1-4 primary or secondary alkyl group or C
_{6-8 are} aromatic groups) heterocyclohexylidene bisphenol. 2. The heterocyclohexylidene bisphenol according to claim 1, wherein X is S. 3. The heterocyclohexylidene bisphenol according to claim 1, wherein X is SO. 4. The heterocyclohexylidene bisphenol according to claim 1, wherein X is SO ₂ . 5. The heterocyclohexylidene bisphenol according to claim 1, wherein X is N—OCOR. 6. The heterocyclohexylidene bisphenol according to claim 5, wherein R is a methyl group. 7. The formula: Where X is S, SO, SO ₂ or N-OCOR and R is a C _1-4 primary or secondary alkyl group or C
_A polycarbonate comprising _6-8 aromatic heterocyclic hexylidene bisphenol structural units. 8. The polycarbonate according to claim 7, which is a single polycarbonate. 9. The single polycarbonate according to claim 8, wherein X is S. 10. The single polycarbonate according to claim 8, wherein X is N—OCOR. 11. The single polycarbonate according to claim 10, wherein R is a methyl group. 12. The polycarbonate according to claim 7, which is a copolycarbonate. 13. The copolycarbonate of claim 7 comprising units where X is SO and units where X is SO ₂ . 14. The copolycarbonate of claim 12 comprising about 25-75% by number of heterocyclohexylidene bisphenol structural units. 15. The formula: (Wherein each of A ¹ and A ² is a monocyclic divalent aromatic group and Y is A ¹ to A ² depending on one or two atoms.
13. A copolycarbonate according to claim 12, which contains structural units of a type which is a cross-linking group of the type separated from 16. The copolycarbonate according to claim 12, wherein X is S. 17. The copolycarbonate according to claim 12, wherein X is N—OCOR. 18. The copolycarbonate according to claim 12, wherein R is a methyl group.